Benzothiazoleazoaniline compounds



United States Patent BENZOTHIAZOLEAZOANILINE COMPOUNDS James M. Straley and David 3. Wallace, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 5, 1952, Serial No. 318,952

10 Claims. (Cl. 260-158) This invention relates to new azo compounds and their application to the art of dyeing or coloring.

We have discovered that the azo compounds having the general formula:

ZOzS

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 3 to 4 carbon atoms, a cyanoalkyl group having 3 to 5 carbon atoms, a fl-acetoxyethyl group, a carbomethoxymethyl group, a carboethoxymethyl group, a B-carbomethoxyethyl group or a B-carboethoxyethyl group, R represents an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 3 to 4 carbon atoms, a cyanoalkyl group having 3 to 5 carbon atoms, a fi-acetoxyethyl group, a carbomethoxymethyl group, a carboethoxymethyl group, a B-carbomethoxyethyl group, a S-carboethoxyethyl group, a 5,,8-difluoroethyl group, a fi,B-difluoro-n-propyl group, a 'y,'y-difluoropropyl group, a 'y,'y-difluoro-n-butyl group, a 6,6-difluoro-n-amyl group, a 5,5,B-trifluoroethyl group, a -trifluoropropyl group or a 6,6,6-trifluoro butyl group, X represents a hydrogen atom, a bromine atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, an acetamino group, an n-propionylamino group or an n-butyrylanu'no group, Y represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group and Z represents an allyl group or an alkyl group having 1 to 4 carbon atoms, are valuable dyes for coloring textile materials made of or containing a cellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof. They are especially of use for the coloration of cellulose acetate textile materials and, accordingly, their utility as dyes is described more particularly with reference to the dyeing or coloration of cellulose acetate textile materials. When applied to the aforesaid textile materials, they give scarlet, red, pink, reddish-violet, violet and blue dyeings. The compounds of our invention also color Wool, silk, nylon, polyethylene terephthalate and modified polyacrylonitrile textile materials similar colors but in general they are not as good dyes for these latter materials as they are for cellulose acetate.

It is an object of our invention to provide new azo compounds. Another object is to provide a satisfactory process for the preparation of our new azo compounds. A further object is to provide dyed textile materials, es pecially cellulose acetate textile materials, which have good fastness to light and gas.

By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, we mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose Patented Mar. 12, 1957- ice bntyrate, cellulose acetate propionate and cellulose acetate butyrate.

The new azo compounds of our invention are prepared by diazotizing a 2-amino-6-(alkyl or allyl) sulfonylbenzothiazole having the formula:

ZOzS

and coupling the diazonium compound obtained with a compound having the formula:

R, R1, X, Y and Z in the foregoing formulas have the meaning previously assigned to them.

The 2-amino-6-(alkyl or allyl)sulfonylbenzothiazole compounds used in the preparation of the new azo compounds of our invention may be diazotized in sulfuric acid or mixtures of mineral and organic acids, following which the subsequent coupling reaction can be carried out, for example, in mineral acids or organic acids. However, it is preferred to diazotize the Z-aminobenzothiazole compound in moderately strong sulfuric acid and couple in moderately weak sulfuric acid. When the diazotization and coupling reactions are carried out in accordance with the preferred procedure, it is usually unnecessary to neutrmize the sulfuric acid in order to obtain the dye since upon sutficient dilution with water the dye-sulfate-is hydrolyzed and the free dye precipitates in solid form. This is a considerable advantage over the use of an organic acid in coupling because the organic acid usually has to be neutralized with the result that the dyestufi is first released in an oily or sticky state from which it is difficult to obtain the dyestuif in a pure form.

2-amino-6-(alkyl or allyl)sulfonylbenzothiazole compounds used in the preparation of the azo compounds of our invention are 2-amino-6-methylsulfonylbenzothiazole, Z-amino-6-ethylsulfonylbenzothiazole, 2-amino- 6 propylsulfonylbenzothiazole, 2 amino 6 isopropylsulfonylbenzothiazole, Z-amino-6-n-butyl-sulfonylbenzothi-azole, Z-amino-6-isobutylsulfonylbenzothiazole and 2- amino-6-allylsulfonylbenzothiazole. The use of Z-amino- 6-methylsulfonylbenzothiazole is ordinarily preferred.

Illustrative of the alkyl groups represented by R and R1 are the methyl, the ethyl, the n-propyl, the isopropyl and the n-butyl groups. Illustrative of the hydroxyalkyl groups represented by R and R1 are the fl-hydroxyethyl, the fi-hydroxypropyl, the 'y-hydroxypropyl, the p,-,-dihydroxypropyl, the fi-methyl-,8,'y-dihydroxypropyl and the S-hydroxybutyl groups. Illustrative of the alkoxyalkyl groups represented by R and R1 are the fi-methoxyethyl and the S-ethoxyethyl groups. Cyanoalkyl groups having 3 to 5 carbon atoms are the fi-cyanoethyl, the 'y-cyano-.

propyl and the B-cyanobutyl groups. Alkyl groups represented by Z include, for example, the methyl, the ethyl, the n-propyl, the isopropyl, the n-butyl and the isobutyl groups.

The new azo compounds of our invention are characterized in that they give dyeings on textile materials made of or containing a cellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof, especially cellulose acetate textile materials, which have excellent fastness to light and gas and which particularly excel in brightness. These dyeings possess the further advantages of being fast to sublimation, of being easily dischargeable to pure white shades and of having a good wash-fastness. The red dyes of our invention possess'a slight blue cast'which is very desirable .in' the preparation of attractive combination shades.

The following examples. illustrate the azo compounds.

and a solution of 17.5: parts of sodium nitrite dissolved in 125 parts of concentrated sulfuric. acid was added while maintaining the temperature below --3 C. The reactionmixture resulting was stirred at C. until the diazotization reaction which takes place was complete. The diazonium reaction mixture thus obtained was added with good stirring to a solution of 46.5 parts of N-fl-hydroxyethyl-N-e-cyanoethylaniline in 1250 parts of aqueous sulfuric. acid at 5 C. Upon completion of the coupling reaction which takes place, the reaction product was recovered cn-the filter by filtration and stirred in. 6000 parts of water for 30 minutes. The free dyestutr' was recovered by filtrationpwashed with water until the, washings were colorless and dried at 6.0- C. V 67 to 75. parts of a dye compound having the formula:

Were'obtained. It colors cellulose acetate textile materials brilliant red shades which have' excellent fastnessto light and gas. The dyeings obtained with this dye compound arelikewise fast to sublimation and are easily dischargeable to pure white shades.

EXAMPLE 2v CHaQHzOH CHzCHzCN 57 parts of 2-amino-6-methylsulonylbenzothiazole. werediazotized and the diazonium compound obtained wascoupled with: 50 parts of N-;S, 3 difluoroethyl N'-fl- Diazotization; coupling" and re hydroxyethylaniline. covery ofthe dye compound. formed werecarried; 'out 'in accordance with the generai procedure described in Ex The-dye compound obtained.colors-cellulose acetate textile materials red shadeswhich have-excellent ample. 1.

fastness to light and gas, which have excell'ent'fastness to sublimation and which are easily dischargeahle to pure white shades.

EXAMPLEBv 57 parts. of 2-amino-6 methylsulfonylbenzothiazole were 'diazotizedand the diazonium compound obtained was coupled with 58 parts ofN-B-carbomethoxyethyl-N- B-cyanoethylaniline. Diazotization, coupling and recovery ofthe dye. compound formed were carried' out in' accordance with the general procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials red shades which have excellent fastness to light and gas; which are. fast to sublimation and which are easily dischargeabl'e to pure white shades. v

' EXAMPLE 4 ethyl-N-B-cyanoethylaniline in 80 parts of 50% aqueous V difluoroethylaniline.

. d sulfuric acid at 0 C.'2 C. The reaction mixture was stirred'for'one hourat"0"C.2' C; (i. e: until'the coupling reaction was complete) and then poured into 1000 parts of water and neutralized with sodium acetate. The reaction product precipitated and was recovered by filtration, washed well with water. and dried in a vacuum at 50 C. A good ield of the dye compound having the formula:

. CHrCHzOH om=onon20is r S/ 7 was obtained. It colors cellulose" acetate textile mate- CHQCHQCN rials brilliant red' shades: which have excellent fastness to light and gas, which are fast to sublimation and which are easily dischargeable to pure white shades.

EXAMPLE 5 6.4 parts of 2 -arnino- 6.- allylsulfonylhenzothiazole were diazotized and the diazoniurn compound obtained; was coupled with 5 parts of N-fl-hydroxyethyl-N-p, Diazotization,. coupling and recovery of the dye compoundformed were carried out in accordance withthe procedure described in Example 4. 6.4 parts of a dye compound which colorscellulose acetate textile materials brilliant red shades which have excellent fastness to light and gas; which have excellent fastness to sublimation and which are easily dischargeable to pure White shades were obtained.

EXAMPLE 6 A solution of '48 parts of sodium'nitrite in 250 parts of concentrated sulfuric acid were added to 500 parts of aceticpropionic acids (6:1) below 5 Cf of 2 amino 6 methylsulfonylbenzothiazole were then added. and the reaction mixture-was dilutedlslowly with. l750iparts of acetic-propionic-acids (651)-while maintaining the temperature below 10" C. Upon completion of the. diazotization reaction. which takes place, the diazonium solutionwas added; atL5 'C; to a'solution-of 102. parts of N.-flrhydroxyethyl N- 3 cyanoethyl-m-toluidine; in. 2000 parts: of aceticepropionic" acids (62-1). coupling reaction. which takes" placewas completed by making: the reaction mixture neutral toCongo. redpaper by the addition of sodium acetate or ammonium acetate. Following neutralization, the'reaction mixture was held for l to 2 hours: at 5 C. and thenpoured: into 20 times its volume cold water.v The. sticky reaction product was recovered. on. the filterby filtration, washed wellv with water and; dried: 160pa1ts ofa' dye compound which colors. cellulose acetate textilev materials bright redshades. which are slightly biuer thanrthose obtained-with the. dye compound of. Example. 1.'- were obtained The dyeings' have excellent'fastness:totlight. gas and sublime tion and are easily dischargeab'leh to pure whitesh adesr The acetic-propionic:acidmixture employed inzthis'ex ample. contained 6 parts by volume. ofj acetic acidi to' l part'by volume; of rpropionicacid.

EXAMPLE? 10 parts of Z-amino-6rmethylsulfonylbenzothiazole were dissolved in 30'parts' of formic acid and the resulting solution was-added. with goodstirring, to parts of .45 aqueous sulfuric acid. A solution of..3i'parts of. sodium nitrite; in. 8gp rtsoinwatenwas. added, beneath e ur a o t re ct on a. temp rature below 5. C. Excess nitrous; acidfwasdestroyed. byadding eitherurea-or sulfamic; acid following'which :the' reaction mixture 'wasadded; rapidly. to. a; solution of 10 parts of N-ethyl-N-fi,y-dihydroxypropyhm-toluidine in 500 parts of 5% aqueouszsulfuricacid; The reaction mixture was stirred for 30minutes1while maintaining. the temperature below. -.5' C. andzthen made neutral'to Congoired paperby the addition of sodium acetate. The

142 parts-- The dye compound which precipitated was recovered by filtration, washed well with water and air-dried. 11 parts of a dye compound which colors cellulose acetate textile materials brilliant reddish-violet shades which have excellent fastness to light, gas and sublimation and which are easily dischargeable to pure white shades were obtained.

EXAMPLE 8 EXAMPLE 9 22.8 parts of Z-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 19.5 parts of N,N-di-fi-hydroxyethyl-mtoluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials reddish-violet shades having good fastness properties and good dischargeability.

EXAMPLE 10 22.8 parts of Z-arnino--methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 22.3 parts of N,N-di-fi-methoxyethyl-mtoluidine. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials reddish-violet shades having good fastness properties and good dischargeability.

EXAMPLE 11 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 24.6 parts of N,N-di-fi-hydroxyethyl-3- chloro-6-methoxyaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials violet shades having good fastness properties and good dischargeability.

EXAMPLE 12 22.8 parts of Z-amino-o-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 23.8 parts of N,N-di-p-hydroxyethyl-macetylaminoaniline. Diazotization, coupling and recovery ofthe dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials reddish-violet shades having good fastness properties and good dischargeability.

EXAMPLE 13 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 32.2 parts of N.N-di-;3,;9-difiuoroethyl-3- acetylamino--ethoxy aniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials violet shades having good fastness properties and good dischargeability.

6 EXAMPLE 141 22.8 parts of 2-amino-6-methylsulfonylbenzothiaiole were diazotized and the diazonium compound obtained was coupled with 22.5 parts of N-fi-hydroxyethyl-N-B- cyanoethyl-m-chloroaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Ex-- ample l. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 15 22.8 parts of 2-arnino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 14.6 parts of N-B-cyanoethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials scarlet shades having good fastness properties and good dischargeability.

EXAMPLE 16 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 19.9 parts of N,N-di-18-cyanoethylaniline. Diazotization, coupling and recovery of the dye compoundformed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials scarlet shades having good fastness properties and good dischargeability.

EXAMPLE 17 22.8 parts or 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 20.4 parts of N-fi-methoxyethyl-N-pcyanoethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example'l. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 18 24.2 parts of 2 amino 6 ethylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 20.1 parts of N-fi-hydroxyethyl-N-5,B- difluoroethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 19 25.6 parts of 2-amino-6-isopropylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 19 parts of N-,B-hydroxythethyl-N-B- cyanoethylaniline. Diazo'tization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 20 25.4 parts of 2-amino-6-allylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 23.2 parts of N-fi-carbomethoxyethyl- N-p-cyanoethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

Monroe 25A; parts 10f 'ihami'no deallylsulfonylbenzothiazole werediazdtized', and the diazonium compound obtained was coupled with 20:4 parts of 'N-o-me'thoxyethyl-N-pcyano ethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in ac-' cordance. with the general procedure described in' Example 1'. The dye compound thus obtained colors cellulose acetate textile materials red shades having good-fastness properties'and good dischargeability.

EXAMPLE 22 27 parts ofv 2- amino-6-isobutylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with- 19 parts of N-fi-hydroxyethylN- cyanoethylaniline. Diazotization, coupling and recovery of the'dye'compound' formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials'red shades having good fastness properties and good dischargeability.

V'EXAMPLE 23" f 5 .Zifi parts. of Z-amino-6en-propylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 19 parts of N-B-hydroxyethyl-N-pcyanoethylaniline. .Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 24 27 parts of Z-amino-6-n-butylsulfonylbenzothiazole were dlaZOIlZGdI and the diaz oniumjcompound obtained was coupled with 19 parts of N-B-hydroxyethyl-N-pcyauoe l ylaniline, Diazotization, coupling and recovery of thedye compound formed were carried out in accord ance with the general procedure'descrihed in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXANL LE 25 EXAMPLE 26 228- parts of Z-arnino-d-methylsulfonylbenzothiazole were diazotized and the diazoniurn compound obtained was coupled with 21.8v parts of N-e-hydroxybutyl-N-fi cyanoethylaniline. Diazotization, coupling and recovery of the .dye compound formed were carried out in accprdance with the general procedure described in Ex ample l. 'The dye compound thusobtained colors cellulose acetate' textile mategials, reds shades having good fastness properties and good dischargeability.

22.8 parts of"2-amino G-methylsultonylbenzoth-iazole were d'iazotized and the diazoniurn compound obtained was coupled with 20.9 parts of N'fl-ethoxyethylj-N-fihydrox yethylani'line." Diazotization, coupling and ;recovery ot the dye compound formed were carried outin accordance with the general-procedure described in *Ekample l. The dyecompound thus 'ohtainedeolbrs'cello 8 p lose acetate textile materials redehadeshavlng: fastness properties and good -elischargezlaili(y2 E A LE 2.

22.8 parts. of 2-amino 6-methylsulfonylbenaothiagiqle were diazotized and the diazonium compound obtained was coupled with 21.8 parts of N-a-cyanobutyl N fl hydroxyethylaniline. Dlazotization, coupling and recovery of the dye compound formed were carried 'outj n accordance with the general procedure described Example 1. The dye compound thus obtained colors; cellulose acetate textile materials red shades having-good, fastness properties and good dischargeability. V a 7 EXAMPLE- 29 V 22.8 parts of 2-amino-6rnethy1sulfonylbenaothiazole were diazotized and the diaaonium compound obtai d was coupled with 19.3 parts of N n-butyl-N-p-hydroxy; ethylaniline. Diazotization, coupling and recovery of a the dye compound formed were carried out in accordance with the general proceduredescribed in Example 1'. The. dye compound thus obtained colors cellulose acetate textile materials reddish-violet shades having goodfastness properties and good dischargeability;

EXAMPLE 30 22 .8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 23.3 parts of N-p-acetoxyethyl-N-ghydroxyethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials reddish-violet shades having good fastness properties and good dischargeability.

EXAMPLE 31 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained; was coupled with 21.8 parts of N-carbornethoxymethyh N-fi-cyanoethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thusobtained colors'cellulose acetate textile materials red shadeshaving good fastness properties and good dischargeability. I

EXAIVIPLE 32 22.8 parts of Z-amino-6-rnethylsulfonylbenzothiazole were diazotized and the diazonium compound obtained" was'coupled with 23.4 parts of N-fi-carboeithoxyethyl-N- p-cyanoethylaniline. Diazotizatiom coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example l. The dye compound thus obtained colors cellulose acetate textile materials red shades havipg gopd fastness properties and good'dischargcability.

EXAMPLE 33 EXAMPLE 34' 22.8 parts of 2-amino 6 methylsulfonylbenzothiagole were diazotized and the diazonium compound oftrtained was coupled with, 21.5 parts of N--;,'y-difiuoropropyl.-1{

fihydroxyethylaniline. Diazotization, coupling and re; cover-y of the dyccompound formed werecarried gigglin accordance with the general procedure described-in Ex ample 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 35 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and thediazoniurn compound obtained was coupled with 22.9 parts of N-- -difluoro n-butyl-N- fl-hydroxyethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in E ample l. The dye compound thus obtained colorsrcellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 36 a 22.8 parts of Z-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 24.3 parts of N-6,6-difiuoro-n-amyl-N-fihydroxyethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 37 22.8 parts of 2-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 21.9 parts of N-fi,fi, 3-trifluoroethyl-N- fl-hydroxyet'nylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 3 8 22.8 parts of Z-amino--methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 23.3 parts of N-- ,'y,'y-trifluoropropyl N-fl-hydroxyethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 39 22.8 parts of 2-amino-d-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 24.7 parts of N-5,5,6-trifluorobutyl-N- ,B-hydroxyethylaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in EX- ample 1. The dye compound thus obtained colors cellulose acetate textile materials red shades having good fastness properties and good dischargeability.

EXAMPLE 40 EXAMPLE 41 22.8 parts of Z-amino-6-methylsulfonylbenzothiazole were diazotized and the diazonium compound obtained was coupled with 22.2 parts of N-fi-hydroxyethyl-m-m butyrylaminoaniline. Diazotization, coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 1. The dye compound thus obtained colors cellulose acetate textile materials reddish-violet .shades having good fastness properties and good dischargeability.

The compounds tabulated hereinafter further illustrate the compounds of our invention. These compounds are prepared by diazotizing the diazo components named hereinafter and coupling the diazonium compounds obtained with the coupling component-s named hereinafter.

The color given is that which the compounds color cellulose acetate textile materials. The diazotization, coupling and recovery operations are carried out in accordance with the procedure described hereinbefore.

Table I DIAZO COMTPONENI: 2-AMINO-G-D/IETHYLSULFONYLBEN- ZOTHIAZ OLE Coupling Component Color 1 N-EB-difluoroethyl-N-n-butylaniline red. 2 N 6, 5 difiuoroethyl N 5, dihydroxy- Do.

propylaniline. N-ethy l-N-fi-hydroxyethyl-m-toluidine reddish-violet. N-fl-cyanoethyl-N-B-acetoxyethylaniline red. N-fi-hy droxyetllylaniline pink. N-fi-hy droxyethyl-m-toluidine reddish-violet. N 3 hydroxyethyl N B carbomethoxpink.

yethylaniline. N-methylaniline red. N-n-propyl-N-B-hydroxyethylaniline reddish-violet. N-n-butyl-N-fi-hydroxyethylaniline Do. N B eyanoethyl N -B hydroxycthyl m red.

bromoaniline. N ,B cyanoethyl N -13 hf; droxyethyl m reddtsl'vviolet.

ethylaniline. N B cyanoethyl N B hydroxyothyl m Do.

methoxyaniline. N B cyanoethyl N -B hydroxypropyl-m Do.

ethoxyaniline. N B cyanoethyl N 5, dihydroxyprored.

pyl-o-toluidine. N B cyanoethyl N B hydroxyethyl o 0.

ethylaniline. N 5 oyanoethyl N fl hydroxyethyl 0 o.

methoxyaniline. N B cyanoethyl N -15 hydroxyethyl o Do.

ethoxyaniline. N,N di B hydroxyethyl 2,5 dimethoxyviolet.

aniline. N,N di 8 hydroxyethyl 2 methyl 5 Do.

methoxyaniline. N,N di 6 cyanoethyl 2 methoxy 5 reddish-violet.

methylaniline. N B cyanoethyl N B hydroxyethyl 2 violet.

methoxy-5-brornoaniline. N,N di B hydroxyethyl 2 ethoxy 5 Do.

chloroanlliue.

Table 2 DIAZO COMPONENT: Q-AJ' INOfi-ETHYLSULFONYLBEN Z OTHIAZ 0 LE Coupling Component Color N N-di-B-hydroxycthyl'm-toluidine reddishwlolet. N,N di -5 hydroxyethyl 2 methoxy 5 blue.

acetylaminoaniline. N,N-di-B-earbomcthoxyethylantline reddish-violet. N B carbomethoxyethyl N 5 cyanored.

ethylaniline. N -methoxyethyl N ,8 cyanoethylani- Do.

e. N -B ethoxyethyl N ,8 eyanoethylanillne. Do. N fi hydroxyethyl N v @1535 trifiuoro Do.

ethylanillne. N 8 hydroxyethyl N 5,5,3 trifluoro- Do.

butylaniline. N B hydroxyethyl N 6.5 difiuoron Do.

amylanlline. N difluoropropyl N -49 -eyanoethyl- Do.

aniline.

V 3 1721512535 Table 7 enro doM-PoNnNT: mmmo-shrsorrtorYLsveroNYr;- DIAZO COMPONENT @fifigggh 'BENZOTHLA-ZOLE Coupling Component Color Coupling Component Color N',N dl-fl-hydroxyethylaniline red. N,N di-fl-carbomethoxyethylaniline reddish-violet. ,llg-di-fl-hydrorytethyl-zu-toluidinev regdishwiolot. N -}fihydruoxyethyl N -ficyanoethyl -m red. e {-di- -'c anoet ni.ine re c oroan me; p o N5 cgrb dmethogygthyb N ethylaniline, D0. N-fi-methowethyl-N-ethylaniline reddish-violet.

. N #91318 difluoroethyl N -5 -"iydroxyethyl- Do. N ndroxyethyl -N -fl-cyanoathyl -m pink. an inc. to uioine. v 64.--. 1 N',N --.di --;8 hydroxyethyl ltt-hloro 0 violet. N ,5 drfluoroethyl-h4-fi-hyd1'0xyothylm- V Do.

methoxyamlme. toluidine. N,N di B hydroxyethyl- 3'- bromo 6 Do. N fl,fl,,6 trifluoroethyl l 3 hydroxy Do.

methoxyamhne. ethyl-m-toluidtne. N-fJ-cyanoethyl-N49-111ethtuq-ethylamline red. N,N-d1-/3-cyan0ethy1an1lme Scarlet. N-B-cyanoethyl-N-Bethoxyethylaniline o-.. Do; N-B-hydroxyethyl-N-B-cyanoethyl-m pink.

N -g i cyglrxlloethyl N B carbomethoxy- Do. ethylamhne.

at y an e. N 11: eyanopropyl NV e carboethoxy- 13-0.

e y niline. Nflmydmyethylanflme pink hl OMwf that the preparation or the azo compounds of N-fl,fi-difluoroethylaniline red. our invention may be entirely clear, the preparation of certainintermediates used in their manufacture isde- T bl 4 scribed hereinafter.

a 6 Preparation of 2-amina-6-methylsulfonylbenzothiamaze COMPONENT: Z-AMINO-S-N-PR'OPYLSULFONYL n of 0 Parts 01 bmmme 111 300 P BENZOTHIAZOLE of acetic acid was added over the course of about 1 hourto a mixture of 171 parts of p-aminophenylmethylsulfone Coupling Component 001m and 202 parts of sodium thiocyanate in 1750 parts of acetic acid. The temperature was held below 35 C. 1 N-fl-cyauoethyI-Yfl-methomethylaniline red. ti a com l t d V f e 2 N -fi cyanoe-th yl N -;3 -ai'h0tnethoxy Do. during the i d1 ajfter p a i n 0 th cihylaniline, bromine-acetic acid mixture, the reaction m1xture was 3 i "l ll l'eddl'sh'violetstirred for 18 hours. The reaction product was recov- 4 I\ ,l\-d1-5- eyan0ethylamlme red. d h filt b fil h d h ti 5 h4i?-difltioroethyl-N-fihydrorryethyl- Do. ere on t e er y tratlon, was e wit ace 0 act an: me. 6 NN di B hydroxyethyl ammo 6 violet and then dlspersednn 6000 parts of water. The reaction ethoxyaniline. 7 mixture thus obtained was heated to bOlllDg and then, 2 52 hydmyethyl2'5'd1mtmXY' I 7 an alkali such as caustic soda or sodium carbonate was s N w ee irifluoroethyl N -s hydrory 7 red. added until the pH'or' the reaction mixture was about 6.

ethy ani he. 7 t 0 N 3 hydmwcthy] N a mrbuethmy D0. The reaction mixture was then cooled, filtered and the ethyleuilino'. reaction product WhlCh collected on the filter was washed well with water and dried at 120 C. 145 to 160 parts Tab] 5 of 2-amino-G-methylsulfonylbenzothiazole were obtained 6 as light yellow crystals melting at 226 C.228 C. DIAZO COMPONENT. 2 AM-INO 6 ISOBUTYLSULFONYL Preparation of. 2-acetylamin0-6-thi0cyan0benzothia- BENZOTHIAZOLE z0le.-To a solution of 18.6 parts of aniline and 304' 7 parts of ammonium thiocyanate in 300 parts of acetic Coupling Component 'Q acid at 15 C. 14.2 parts of chlorine were bubbled in at 15. C.-17 C. 30 minutes after addition of the 1 hYdYOXYQth-YI vm flcetyl reddish-Violetchlorine 15.6 parts of sodium acetate and 30.4 parts of 2 -,g ,l,g l im .N g. a g mt ammonium thiocyanate were added to the reaction mixam 1110. 3 n N,N di fl hydmxyethy1 2 methoxy 5 blue ture. W h lle holding the temperature of the reaction acetylaminoaniline. mixture below 35 C., 14.2 parts of chlorine were passed 4 i f gg in and the reaction mixture was stirred overnight'at room 5 N -f-lcyali1oethyl N -e werhomethoxy on. temperature. The solid present in the reaction mixture at 3 ani ine. 6 N,N-di-fl-hydr xyethyi-m-phloroaniline.... reddish-violet. f qw by filtration waghed Wlth 50 Parts of 7 N-tgg fi ltrifluoroethyl -N -5-hydroxy red. acetic acid and then suspended 111 600 parts of water.

e yani ine. 8 Nmy?mfiuompmpyl N fi hydmxy The mixture thus obtained was heated toboillng and ethylaniline. filtered. 30 parts of sodium acetate were added to the filtrate and the solid which precipitated was collected at Table 6 C. on a filter, washed with 200 parts of cold water and dried at 100 C. 30'parts of a product melting at vmzo COMPONENT: Z-AMINO-B-NJBUTYLSULFONYL 3 ef thuspbiam'idr BENZOTHIAZOLE 60 30 parts of acehcanhydrrde were added at C. to .a: V solution of 52.6 parts of the above product in 81 parts of Coupling Component Color acetic acid, and the temperature of the reaction mixture was held at 80 C.- C. for one hour. The reaction 3 NN di-fieyanoothylaniline 1ed.D mixturewas then poured into 1000 parts of cold water 5: IR 7 3: 05 and the product. which precipitated was recovered by tacre-nearb -Inethoxyethylaniline go; filtration, washed with 500 parts of water andthen dried fggg 'Nscarboetmxyetm'l' at 60 C. 62 parts of 2-acetylamino-G-thiocyanobenzo- A fiyg y thylm-tgnda reddlgsh-viole thiazole melting at 247 C.249 C. were thus obtained. 'j if t ggfi jf figggi gfi red, 0 Preparatzon of 2-ammo-6-ethylsulfortylbenzothzazole. \Iallllallglg. rm yet 1 \1 g h (hex 70 A solution of 26.4 parts of crystalline sodium sulfide i hg fi fi my y y 7 and 24.9 parts of 2-acetylamino-6-thiocyanobenzothiag f l P- zole in parts of ethyl alcohol were refluxed together N-fi-cyanoethylanilme ana scarlet. I l'-;9,B,d1fluoroethylamlme Do, for 10 minutes and after cooling the reaction rmxture to N'fififlelriflumoethylflmlme 20 C l6.3 partsof ethyl iodide were added at onetime and the reaction mixture resulting was refluxed for'one hour. The reaction mixture was then poured into 1000 parts of Water and the product which precipitated was recovered by filtration, washed well with water and dried at 60 C. 23.6 parts of Z-acetylamino-6-ethylthiobenzotbiazole melting at 168 C.169 C. were obtained. If desired, the quality of the product can be checked by hydrolyzing a little of the product with acid to 2-amino-6- ethylthiobenzothiazole melting at 137 C.139 C.

19 parts of 30% aqueous hydrogen peroxide were added to a solution of 15.5 parts of 2-acetylamino-6- ethylthiobenzothiazole in 53 parts of acetic acid while maintaining the temperature of the reaction mixture between 80 C.-90 C. The reaction mixture was maintained at this temperature for one hour and then poured into 500 parts of cold water. The solid present in the reaction mixture was recovered by filtration and then suspended in a mixture of 800 parts of water and 100 parts of concentrated hydrochloric acid. The reaction mixture thus obtained was heated to boiling and then filtered. The filtrate was neutralized with sodium acetate, cooled to 25 C. and filtered. The product collected on the filter was washed with cold water and dried at 60 C. 8.5 parts of 2-amino-6-ethylsulfonylbenzothiazole melting at 173 C.-175 C. were thus obtained.

Preparation of 2-amin0-6-is0propylsulfonylbenzothiazle.This compound was prepared in accordance with the procedure described for the preparation of 2-amino-6- ethylsulfonylbenzothiazole using 17.76 parts of isopropyl iodide in place of ethyl iodide. The melting point of the 2-acetylamino-G-isopropylthiobenzothiazole formed during the process was 174 C.--175 C. while that of the final product 2-amino-6-isopropylsultonylbenzothiazole was 207 C.-209 C.

2-amino-6-n-propylsulfonylbenzothiazole is similarly prepared by the use of 17.76 parts of n-propyl iodide in place of isopropyl iodide in the foregoing example.

Preparation of Z-amin0-6-is0butylsulfonylbenzothiaz0le.This compound was prepared in accordance with the procedure described for the preparation of Z-aminofi-ethylsulfonylbenzothiazole using 14.3 parts of isobutyl bromide in place of ethyl iodide. The melting point of the Z-acetylamino-6-isobutylthiobenzothiazole obtained was 167 C.l68 C. while that of the final product 2- amino-fi-isobutylsulfonylbenzothiazole was 206 C.-207 C.

Z-amino-6-n-butylsulfonylbenzothiazole is similarly prepared by using 14.3 parts of n-butyl bromide in place of isobutyl bromide in the foregoing example.

Preparation of 2-amin0-6-allylsalfonylbenzothiazole.-- This compound was prepared in accordance with the procedure described for the preparation of 2-amino-6- ethylsulfonylbenzothiazole using 12.7 parts of allyl bromide in place of ethyl iodide. The melting point of the 2-acetylamino-6-allylthiobenzothiazole obtained during the process was 170 C.-171 C. while that of the final product 2-amino-fi-allylsulfonylbenzothiazole was 172 C.174 C.

The azo dye compounds of our invention can be applied to the textile materials named hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignin sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.-90 C. and maintained at this temperature until dyeing is complete, usually onehalf to two hours. From time to time throughout the dyeing operation, the material 1s worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

Widelyyarying amounts of dye can be used in the dyeing operation. The amount of dye used can be} for example, $6 to 3% (by weight) of that of the textile material although lesser-or greater amounts of dye can be employed.

We claim:

1. The azo compounds having the general formula:

wherein R represents a member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxylalkyl group having 3w 4 carbon atoms, a cyanoalkyl group having 3 to 5 carbon atoms, a B-acetoxyethyl group, a carbomethoxymethyl group, a carboethoxymethyl group, a B-carbomethoxyethyl group and a B-carboethoxyethyl group, R1 represents a member selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 3 to 4 carbon atoms, a cyanoalkyl group having 3 to 5 carbon atoms, a fi-acetoxyethyl group, a carbomethoxymethyl group, a carboethoxymethyl group, a B-carbomethoxyethyl group, a B-carboethoxyethyl group, a 5,13-difiuoroethyl group, a [3,;3-difluoro-n-propyl group, a 'y,'y-difluoropropyl group, a -difiuoro-n-butyl group, a 6,6-difluoro-n-amyl group, a 8,5,{3-trifiuoroethyl group, a -y,'y,'y-trifiuoropropyl group and a 6,6,6-trifiuorobutyl group, X represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, an acetamino group, an n-propionylamino group and an n-butyrylamino group, Y represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a methoxy group and an ethoxy group and Z represents a member selected from the group consisting of an allyl group and an alkyl group having 1 to 4 carbon atoms.

2. The azo compounds having the general formula:

cmcrucN wherein Z represents an alkyl group having 1 to 4 carbon atoms.

3. The azo compounds having the general formula:

i CHaCHsCN S CH3 CHzCHiOH wherein Z represents an alkyl group having 1 to 4 carbon atoms.

4. The azo compounds having the general formula:

CHeCHsOH CHQCHIOH 

1. THE AZO COMPOUNDS HAVING THE GENERAL FORMULA: 